DE3229635A1 - Surgical bonding systems for uniting endogenous hard tissue if required with plastic and/or metal - Google Patents

Abstract

A surgical bonding system suitable for uniting endogenous hard tissue contains as polymerisation initiator an organoboron compound and an absorbable (meth)acrylate component which is liquid to solid at room temperature and consists of (meth)acrylic esters with (meth)acrylate residues on polyester oligomer chains composed of hydroxy carboxylic acids, there preferably being two (meth)acrylate residues in alpha , omega position, and the polyester oligomers being formed from monohydroxy monocarboxylic acids.

Description

Surgical binder systems for gluing

of the body's own hard tissue, if desired with plastic and / or Metal The invention relates to new, self-hardening under the influence of atmospheric oxygen Plastic systems that are used as surgical binders or adhesives for gluing of the body's own hard tissue and / or for the in-situ formation of plastic molded parts in the.

Use in the course of surgical work in human and veterinary medicine can find. A special feature of the new ones made by means of the invention Plastics lies in their resorbability through the body's own degradation reactions, if desired, the duration of the resorption process can also be influenced can be.

To the state of the art The firm, permanent union of separate Bone parts or the fixation of artificial implants in or on the bone or tooth material is an old wish of surgeons. So far are predominantly Polymethacrylate, epoxy resin and polyurethane systems have been investigated. In practice So far, only polymethacrylates have prevailed. They are predominant suitable for the implantation of gel prostheses, the cement-metal Osteosynthesis, Spinal fusions and defect coverings on the roof of the skull or implantation of Support material in facial surgery.

In addition to these applications, there is a desire for additional fields of application for bone adhesives or

To develop bone cements, for example in connection with anatomical reduction, fixation and retention of bone fragments Debris or joint fractures. The aim is, in particular, a permanent one Association of bone fragments with the aim of immediate resilience the hardening of the cement or adhesive.

Reversible reduction and fixation appear particularly desirable and retention of bone fragments using absorbable adhesive systems.

Here the bone adhesive or cement should be synchronized with the formation of new bone be absorbed by the body.

The reversible stabilization of fractures is also important by means of plates or splints that are attached using absorbable adhesives Here, when using rails or plates made of metal or plastic there is no need to drill holes in the bone or to use screws will. When using absorbable support materials e.g. made of polylactic acid or Polyglycolic acid could also dispense with the second operation.

Adhesives or cements for such purposes include the following To make demands: chemical stability, preservation of the physical properties societies even under the influence of body fluids, within the required time Framework, biological compatibility, no carcinogenicity, no allergy triggering or so. annoying hypersensitivity, full mechanical load capacity after hardening, in-situ production of plastic parts in the desired shape, good sterilizability, adequate setting time, as little change in volume as possible and heat generation when setting.

Plastic materials apply especially to the area of resorbent urine the additional requirements of absorbability in the given time frame the body's own degradation processes as well as freedom from harmful secondary reactions Degradation products.

The methacrylate systems that have only been used up to now exist from the following components: one or more radically polymerizable Monomers a radical initiator system to initiate polymerisation for polymers Cohesion improvement and for adjusting the viscosity of (active) fillers Improvement of the mechanical properties.

In addition to methyl methacrylate, there are combinations of polymerizable monomers with methacrylic acid numerous other systems have been included, of which some have gained practical importance - cf.

on this J.M. Antonucci, Polymer Science and Technology 14, 357 cm 981). Also on the side of the hardener systems for methacrylate systems that polymerize at room temperature there is a wide range of accelerators available today - cf. for example G.M. Brauer, Org.Coat. Plastic Chem. 42, -321 (1980) and J.W. Prane, Org. Coat. Plastic Chem. 40, 338 (1979) - nevertheless there are also improvements here desirable.

It is known that the adhesion of methacrylate adhesives Bone material can be increased by boron alkyl hardeners. Boron alkyl compounds e.g. triethyl, Tripropyl and tributyl boron dissolve free radical polymerizations in the presence of atmospheric oxygen the end.

They are therefore also suitable as hardeners for 2-component methacrylate adhesives see JA-OSen 42 14 318 and 45 29 195 as well as DE-OS 23 21 215.

JA-OS 42 4 318 proposes trialkyl boron as a hardening agent for dental medicine Binders and fillers. With trialkyl boron strengths result, as previously could not be achieved with other hardening agents. Apparently The reason for this is that trialkyl boron triggers graft polymerization on collagen - see Shikai-tenbo, 32, 609 (1968). The adhesive or the filler material adhere via a covalent chemical bond to the dentin.

The use of trialkylboron compounds such as trimethyl, triethyl, However, tripropyl and / or tributyl boron is associated with exceptional safety problems and application-related difficulties.

For example, triethyl boron has an ignition temperature of -20 ° C.

To avert these serious disadvantages, it has been proposed that To implement trialkylboron compounds with amines or with defined oxygen quantities - see JA-OS 45-29 195 and DE-OS 23 21 215.

However, this does not make these systems self-igniting prevented. The ignition temperature is only in the temperature range from 0 to 70 ° C shifted. As a result, the production of larger quantities of adhesive is still possible impossible and their scope limited.

For improving cohesion, for setting more favorable in application terms Viscosities and to reduce volume contraction during curing is it is known to add polymers to the monomer, e.g. polymethyl methacrylate, Polychloroprene, chlorosulfonated polyethylene, nitrile rubbers and / or polyurethanes See U.S. Patents 3,333,025, 3,725,504, 3,832,274, 3,890,407 and 3,994,764.

It has continued to improve hardness and dimensional stability found to be beneficial to add fillers in finely divided form, crystalline Systems are clearly amorphous fillers due to their high packing density consider, see A.K. Abell et al. Pole. Sci. and Technology, 14: 347 (1981).

Both the monomers used in the adhesive system and the the starter system used in each case affects the strength of the adhesive bond. When bonding hard tissue in medicine, the strength achieved depends on it additionally heavily on the pretreatment of the bone material and the storage conditions of the joined parts. For the use of adhesive systems in the organism are Strength measurements on defatted dry bone tissue are not very meaningful. The bonding of moist and greasy products that have not been pretreated appears to be more relevant Bones and the strength measurement on the test specimens obtained after storage in (Blood) Ringer's solution. Conventional ones achieved under these simulated in vivo conditions Methacrylate adhesives and bone cements on bone material tensile strengths -2 of approx. 60 Ncm 2 (compare G. Giebel et al.

Biomed. Techn. 26, 170 (1981)). These strength values are for a Range of applications, for example for the union of bone fragments with the aim of an immediate load-bearing capacity after hardening of the cement resp. Adhesive is clearly too low. The aforementioned result from this Limitations in the applicability of bone cement.

Finally, it is known that certain plastic masses in the living Organism are broken down.

For example, thread material that can be absorbed in the organism is commercially available based on polyglycolic acid or polylactic acid. Also uses of this material in dentistry and orthopedics are known. To the degradability of the polymers lies extensive data material, see for example R.A. Miller et al. J.Biomed, Mat. Res. 1977, 11, 711-719; D.C. Miln et al, Scot. med. I, 17, 108 (1972) as well as AT THE. Reed et al. Polymer 24, 499 C1981). By co-condensation of glycolic acid and Lactic acid can set the rate of degradation as desired within wide limits , see the literature reference mentioned first above.

Polyglycolic acid is usually made from glycolic acid via the intermediate stage of Gl-olids with suitable catalysts at temperatures in the range from 180 to 200 ° C. The direct polycondensation of glycolic acid at 118 ° C and 5 mbar leads to oligomeric products of low cohesion - see A.M. Reed et al. loc.

For use in medicine 21o J glue or cement come Polyglycolic acid and / or polylactic acid so far out of the question. Adhesives and cements are characterized by the application of a liquid form, which after application leads to the solid polymer. Because of the high reaction temperatures required is the in-situ generation of polyglycolic acids and polylactic acids in the organism for Connection of substrates not possible.

OBJECT OF THE INVENTION The object of the present invention is to provide of adhesives or self-curing plastic compounds for use in the Medicine that is characterized in particular by the combination of the following properties distinguish: high cohesion and at the same time good adhesion to moist and greasy Surfaces and degradability of the hardened plastic masses in the organism, in particular with a controllable rate of degradation.

In a broader sense, the object of the invention is for the surgical Working in the field of human and veterinary medicine, curable plastic compounds are available to be used as adhesive systems for bonding the body's own hard tissue for example bones - if desired also with exogenous materials, such as Plastic or metal - are suitable. These curable plastic compositions should but also suitable for the in-situ production of individually designed molded parts be.

Subject matter of the invention The subject matter of the invention is accordingly in a first embodiment, one suitable for gluing the body's own hard tissue Surgical binder system based on a polymerizable (meth) acrylate adhesive and a polymerization initiator, this system being characterized is that it is a resorbable CMeth) acrylate component which is liquid at room temperature to solid (meth) acrylic acid esters lait (meth) acrylate residues from hydroxycarboxylic acids Contains formed polyester oligomer chains and continues to act as a reaction trigger for the polymerization resp.

Hardening reaction organoboron compounds are provided. object the invention is also the use of such binder systems for gluing of the body's own hard tissue, for example bones with one another, if desired but also with foreign materials such as plastic or metal.

Another object of the invention relates to the use of Binder systems of the type described for the in-situ production of individual formed molded parts, in particular in connection with the gluing of the body's own Hard fabric, possibly together with plastic andZ or metal.

Polymerizable (meth) acrylate component As an essential ingredient the binder systems according to the invention are reactive monomers on acrylate or methacrylate base; - In the context of the description of the invention as (meth) acrylate compounds referred to - used, whereby in particular the speaking Methacrylate compounds are of particular importance. These not previously described reactive (meth) acrylate compounds are the subject of the earlier German patent application D 6529 (P 32 04 504.2). They excel when used in adhesives a number of desirable properties. For example, you own due to their low vapor pressure has low volatility. Despite a comparatively high level Molecular weight gives them the option of being liquids at room temperature or at least to form viscous spreadable pastes. They are easy to mix. with the other components of the binder systems usually used.

They can be used to achieve high-strength, elastic adhesive connections. In particular, however, these reactive monomers selected according to the invention lead to hardened plastics that can be absorbed by the living organism. Their use in the context of surgical work thus leads to reversible training of gluing, support or. Bracket elements and the like, for example have a temporary effect on bone fractures, but ultimately again be broken down by absorption.

The gMeth) acrylate derivatives used according to the invention contain one or preferably several (.Meth) -acrylate residues on an oligomeric polyester chain, which has been formed from hydroxycarboxylic acids.

Preferred (meth) acrylate compounds are the two CMeth) acrylate radicals on the polyester oligomer segment. These compounds can be used as such can be used. But there are also mixtures of different types of compounds within the scope of the invention, in particular. those from speaking Components with only one (meth) acrylate group and those with two (meth) acrylate groups on the polyester oligomer segment.

In the types with two (meth) acrylate residues, which are more important for practical use These functional groups are preferably located in such terminal positions in the molecule Oligomer segment that the two end units of the oligomer segment each with a (meth) acrylate group ¢; are substituted (oL, £ position}.

The oligomer segments have the structural feature on. By oligomerization, they are suitable hydroxycarboxylic acids or hydroxycarboxylic acid mixtures of the general formula accessible.

In a preferred embodiment of the invention, the radicals are -R- and n selected in this way, or

coordinated that the average molecular weight of the polyester oligomer unit ranges from about 200 to 600. Particularly preferred values for the middle Molecular weights range from about 300 to 500.

The polyester oligomer segment is used in a preferred embodiment of the invention from monohydroxymonocarboxylic acids, d "has a carbon number of about Do not exceed 20 in the molecule and in particular about 10. Polyester igomers from corresponding acids with 2 to 10 especially 2 to 7 carbon Atoms in the molecule can be particularly important.

There can be certain for the formation of the polyester oligomers selected individual hydroxycarboxylic acids or mixtures of different hydroxycarboxylic acids come to use. Particularly important hydroxycarboxylic acids for the formation of this In the middle of the (meth) acrylate compounds used according to the invention are glycolic acid, the isomeric lactic acids, the isomeric isomeric or hydroxypropionic acids, the optionally isomeric -, 4- or t-hydroxybutyric acids, o-hydroxybenzoic acid (Salicylic acid), m-hydroxybenzoic acid and Z or p-hydroxybenzoic acid (anisic acid).

It can both certain isomers of the acids mentioned as any mixtures can also be used.

The polyester oligomers can expediently also be used of monofunctional and Z or, preferably, with the use of difunctional ones Reactants have been prepared that serve multiple functions. On the one hand the control of the average molecular weight is achieved through these reactants used in the polyester oligomers and thus the setting of the desired viscosity ranges enables. On the other hand, through the selection of the functional groups, the one that is also used Co-reactants given the possibility of uniformly terminal on the polyester oligomers Form hydroxyl groups or terminal carboxyl groups, which in itself is a Polymers or

Oligomers of a hydroxycarboxylic acid is initially not the case. Finally, it is possible to use selected monofunctional co-reactants to eliminate a reactive end group of the polyester oligomers, so that at this Type of connections for the subsequent connection of the (Mead) -acrylate residues only have a reactive function. By suitable mixing of monofunctional and difunctional co-reactants it is finally possible predetermined mixing ratios of mono- (meth.) - acrylate compounds and bis- (meth) acrylate compounds.

As monofunctional co-reactants come in particular monoalcohols, Monocarboxylic acids and / or monoamines.

Primary, secondary and Z or tertiary monoamines - contemplated. Difunctional Co-reactants in the preparation of the polyester oligomers are difunctional alcohols or dicarboxylic acids or functional reactive dicarboxylic acid derivatives, for example corresponding anhydrides, esters, halides and the like.

Are oligomers of the type described by cocondensation of hydroxycarboxylic acids and diols are produced, ultimately resulting in polyester oligomers with terminal ends Hydroxyl groups. The amount of diols used is determined - in coordination with the reaction conditions - the average molecular weight of the resulting polyester oligomer. Polyester oligomers with hydroxyl end groups can easily be produced by reaction with acid anhydrides be converted into analogous derivatives with carboxyl end groups. On the other hand the oligomers by cocondensation of hydroxycarboxylic acids with dicarboxylic acids respectively If reactive dicarboxylic acid derivatives are produced, polyester oligomers are formed directly with terminal carboxyl groups or carboxyl group derivatives.

Here, too, the co-reactant used has a unifying effect at the same time refer ';. ch of the terminal reactive groups and molecular weight regulating. In detail, the known knowledge for the production of polyesters respectively applies here Copolyesters.

The use of monoalcohols and / or monoamines leads to preferred blocking of the terminal carboxylic acid group in the polyester oligomer, the use of monocarboxylic acids accordingly blocks the terminal Hydroxyl group side of the oligomer.

In all of the cases described here, modified polyester oligomers are formed, which, in a manner known per se, are easy to the (meth) acrylate compounds to be used according to the invention can be implemented.

If terminal hydroxyl groups are present on the polyester oligomer, so the (meth) acrylic acid group is -bzw by esterification or transesterification. by a comparable reaction - with acrylic acid or acrylic acid esters andZor in particular corresponding methacrylic acid compounds introduced.

However, if terminal carboxyl groups are present in the polyester oligomer before, the desired ones can also easily be found in a manner known per se Attach (meth) acrylate groups. The implementation of, for example, is suitable here oligomeric intermediate with glycidyl esters of acrylic acid or the Methacrylic acid. With splitting of the glycidyl group, the (meth) acrylate group is formed via the glyceride residue to the mono- or dicarboxylic acid formed as an intermediate tied up.

In the selection of those usually only used in subordinate quantities monofunctional or difunctional co-reactants are practically no restriction kungen given. So these reactants can be aliphatic, cycloaliphatic or aromatic Be nature. They generally have a carbon number not above C25, preferably not above C15.

Suitable diols contain, for example, 2 to 20 carbon atoms, preferably 2 to 10 and especially 2 to 6 carbon atoms in the molecule. The same information applies fu the corresponding dicarboxylic acids. Examples of suitable diols are: ethylene glycol, Di-, tri-, tetraethylene glycol, propylene glycol '; .propylene glycol, 1,3-butylene glycol, $ 1,4-butylene glycol, 2,2-dimethyl-1,3-propanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,3-Cyclohexanedimethanol, 1,5-Pentanediol, 1,6-Hexanediol, 1, 10-Decanediol and 2 2-Bis- (3-hydroxycyclohexyl) propane. For converting the oligoester diols into oligoester dicarboxylic acids The following anhydrides are particularly suitable: succinic anhydride, glutaric anhydride, Phthalic anhydride, itaconic anhydride, citraconic anhydride as well as alkenyl succinic anhydrides.

Suitable dicarboxylic acids are, for example: oxalic acid, malonic acid, Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, Sebacic acid, isosebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, Dodecanedicarboxylic acid, phthalic acid, hexahydrophthalic acid, isophthalic acid, terephthalic acid and biphenyl dicarboxylic acid.

The monovalent co-reactants are aliphatic and cycloaliphatic or aromatic monoalcohols, corresponding monocarboxylic acids and optionally corresponding primary, secondary or tertiary amines into consideration. Your C-number can lie within the specified limits.

Of course, in all cases - that is, both Hydroxycarboxylic acids as well as the co-reactants - not just the free ones reactive components of the type mentioned, but also such reactive derivatives are used are, in a known manner under the conditions of the esterification, respectively Transesterification of the desired polyester oligomers of the predetermined molecular weight So, for example, the esters of hydroxycarboxylic acids are suitable, as well as Lactones or lactams of hydroxycarboxylic acids with diols respectively Diol esters can be implemented, in particular transesterified, Both the production of the polyester oligomers takes place as their conversion to the (meth) acrylate compounds in a manner known per se, for example by reaction in the presence or in the absence of solvents, if desired in the presence of catalysts, in particular Esterification catalysts.

Are mixtures of difunctional and monofunctional (meth) acrylate compounds used, so in the preferred embodiment, the content is more monofunctional Components not above 95 mol percent, based on the mixture of monofunctional and the difunctional components. Are preferred Mixtures of named type, in which the content of monofunctional components does not exceed 50 Mol percent and in particular not above 10 mol percent.

In a preferred embodiment of the invention, (meth) acrylate compounds or appropriate mixtures used that flow at room temperature or at least are spreadable pasty, so that they are the main component or even as the sole polymerizable adhesive component in surgical binders can be used. It can be preferred that the liquid (meth) acrylate compounds at room temperature a viscosity in the range from about 500 to 70,000 mPas preferably in the range from about 3000 to 50,000 mPas. Solid (meth) acrylate compounds of the type used according to the invention, however, dissolve well in liquid polymerizable Components, for example in methyl methacrylate, so that also solid connections of the invention in admixture with liquid conventional monomer components in easy way to the processing technology required, liquid adhesive components can be worked up.

Organoboron compounds as initiator components As initiator components organoboron compounds are used for the polymerization and thus curing of the binder systems into consideration, the subject of a number of earlier applications for property rights by the applicant are. What these initiators based on reactive boron components have in common: They have however, show a reactivity comparable to that of the known lower boron alkyls at the same time a significantly reduced tendency to self-ignite.

This enables easy and safe handling. the Organoboron compounds to be used according to the invention indicate during use the air only slows down activity, they can be used as a separate hardener component are used in two-component adhesive systems, is particularly possible but also their use as primers in systems of so-called no-mix adhesives. The boron-containing hardeners used according to the invention lead to high strengths the adhesive bonds or the molded plastic parts formed in situ. At the same time, it is possible to influence the curing speed and thus to adapt to the conditions desired in practice.

The structure of the initiator component ultimately ensures good Adhesion of the adhesive or binding agent to the body's own material.

Hardeners based on organoboron compounds which can be used according to the invention are described, for example, in the published European patent applications No. 81109074.5 (D 6144 EP), No. 81109073.7 (D 6246 EP) are of particular importance however, the organoboron compounds or systems used in the older German patent applications D 6391 (P 31 43 945.4), D 6460 (P 32 Ol 780.4), D 6461 (P 32 01 731.6), D 6517 (P 32 07 @ 64. @) and D 6548 (.P 32 07 263.5) are.

Suitable initiators for the new systems can thus be selected from the following group of boron compounds: a) Boron compounds with sterically hindering alkyl groups of the general formulas where R 'or R is an aliphatic mono- or dicyclic with 3 to 25 carbon atoms and Ro is either H or an optionally cyclic hydrocarbon radical with 1 to 15 carbon atoms, b) boron compounds, the reaction products of dihydroxyaromatic compounds with H3 or their alkylation products are, with the general formula where R1, R2 and R3 represent either H or an alkyl group with 1 to 4 carbon atoms and R1 are R2 can also represent an aromatic and / or alipractical cycle, c) boron compounds of the general formula where R4 represents an alkyl radical having 1 to 6 carbon atoms.

Accordingly, there are numerous known or known boron compounds boron alkyls which can be prepared in a known manner. Typical representatives of such boron compounds are for example 9-Borabicyclo- L3.3 1jnonan Diisopinocampheylboran, Dicyclohex.ylboran, Thexylborane (2,3-dimethyl-2-butylborane), 3,5-dimethylborinane, diisoamylborane. Under of these compounds is the first-mentioned 9-borabicyclo- [3.3.1] -nonane from practical Reasons preferred.

A compilation of the manufacturing options for suitable boron compounds can be found in the monograph Herbert C. Brown, 1975 "Qrganic Synthesis via Boranes", Publisher John Wiley & Sons. as Initiators can still Hydroboration products of dialkylboranes and olefins are used.

Conceivable olefins are butene, isobutene, hexene, cyclohexene, vinyl chloride, Allyl chloride, allylamine or methyl methacrylate, vinyl acetate or methyl crotonic acid. Among the suitable compounds are worth mentioning, for example: Diisopinocampheylbutylboron, Thexylcyclohexylcyclopentylboron, thexyllimonylboron, trinorbornylboron, B-butyl-9-borabicyclo L3 3.1 nonane, B-isobutyl-9-borabicyclo E3.3.1] nonane, B-isobutyl-9-bcbicyclo E3.3.1j nonane, B-E 2- (4-cyclohexenyl) ethyl 3 9-borabicyclo 3.1] nonane, B-cyclopropyl-9-borabicyclo F3 3.1] nonane, B-p-tolyl-9-borabicyclo [3.3.1] nonane, B-tert-butyl-3,5-dimethylborinane. In addition, there are reaction products of 1,2-dihydroxybenzenes such as catechol with hydrogen boride (catecholborane) and tri-n-butylboroxine suitable.

Further particularly preferred initiators or hardeners are described below under d): d) These starter systems of the invention exist from a homogeneous mixture of at least one organoboron compound which can be activated by admission of air with at least one liquid to solid at room temperature, the organoboron compounds towards inert organic oligomers or polymers.

The term “homogeneous mixture” is preferred Understand single-phase mixtures of substances at storage and application temperature, such as they are characteristic of real solutions.

As organoboron compounds are primarily boron alkyl and / or Boraryl compounds wise the corresponding organoborohydride compounds suitable. Boron alkyl compounds or boron alkyl hydrides are special ones suitable class of substances. So come into consideration in the preferred embodiment Compounds of the types: R1R2R3B, R1R2BH and Z or R1BH2, in these general Formulas the radicals R1, R2 and R3 are hydrocarbon radicals, in particular alkyl radicals, which, however, can also contain heteroatoms, in particular 0, N and / or S.

Are there at least two such inorganic ones. Residues on the respective boron atom before, they can in turn be closed to form a ring system. The boron Substituting hydrocarbon radicals have in a preferred embodiment in each case no more than about 30 carbon atoms, preferably no more than about 25 carbon atoms on. It may be preferred that any of these organic radicals on boron no longer exist than has about 12 to 15 carbon atoms.

As a boron-containing initiator component or else suitable for production boron-containing initiator components can, in particular, organoboron monohydride compounds, especially dialkylboronohydrides are used.

A typical representative of such boron compounds is, for example the previously mentioned under a) 9.-Borabicyclo [3.3.1] nonane (9-BBN), which from practical Reasons may be preferred.

In this embodiment, however, simple boron initiators can also be used Trialkylboranes and hydroborination products of mono- or in particular Dialkylboranes and olefins can be used as described above.

Oligomers are suitable as solvents with a very low vapor pressure or polymers that are inert to the organoboron compounds, im The rest are not subject to any restrictions with regard to their structure, provided that there is a homogeneous miscibility between these acting as a solvent Polymer substances and organoborve compounds. Are accordingly suitable all polymers, polycondensates and / or polyadducts which have the specified Satisfy conditions. The average molecular weights of these oligomeric or polymeric solvents can range from 200 to 50,000,000 g / mole. Depending on the structure and molecular weight, these solvents can be Room temperature, low viscosity, flowable to solid. It may be desirable that the mixtures containing organoboron compounds are viscous at room temperature are flowable or spreadable. For the effectiveness of the invention However, this is not a prerequisite for the starter systems used as initiators.

On the contrary, the storage stability of the corresponding at room temperature solid mixtures of substances are particularly good.

Suitable polymeric solvents in the sense concerned here are, for example corresponding polyethers, polyesters, polyamides, polyurethanes, polysiloxanes and the like. For the creation of flowable systems, liquid oligomers can be used at room temperature with viscosities roughly in the range of 1,000 up to 70,000 mPas (room temperature) be particularly interesting. It has been shown that in particular polyester and Polyamides are versatile in the context of the invention. You can - as well like the other polymeric solvents - produced in a manner known per se in the case concerned, for example, by polycondensation of dicarboxylic acids with diols or diamines, optionally with the use of monofunctional ones Reactants for limiting or regulating the average molecular weight. In general, saturated dicarboxylic acids and saturated glycols are preferred here each with up to 15 carbon atoms, in particular with up to 10 carbon atoms in the molecule. Analogue This information also applies to the amines or diamines used in production of polyamides. Suitable polyethers are, for example, polyethylene oxides or polypropylene oxides with molecular weights in the specified range. In detail, the extensive applies here Expertise in polymer chemistry.

The organoboron compounds are used to produce the starter systems with complete exclusion of oxygen in the inert organic oligomers, respectively Polymers dissolved. If necessary, you can work with moderate heating.

For example, it is possible to accelerate the resolution to temperatures of up to 100 ° C, preferably about 70 ° C. When using Oligomers or polymers that are solid at room temperature are also used inert liquid solvent appropriate. The known solvents are suitable here for organoboron compounds in particular tetrahydrofuran or polyethers, such as diethylene glycol dimethyl ether but also esters, halogenated hydrocarbons and like that. Under With the use of these liquid auxiliaries, intimate mixtures are produced, the auxiliary liquids can then be drawn off and then the boroalkyl / oligoir mixtures to be isolated. It is best to store them in a closed vessel, preferably under inert gas, for example under nitrogen.

The content of organoboron compounds in such starter systems is usually not more than about 70 weight percent, and preferably not more than about 50 percent by weight - each based on the total weight of the mixture. It is still preferably that the content of organoboron compound is at least about 1 percent by weight of the overall system, so that amounts of about 1 to 50 percent by weight in particular 3 to 50 percent by weight are particularly suitable.

Another possibility that is important in practice is used as an initiator component Polymeric organoboron compounds stabilized against ingress of air, which are described below under e) are described: e) The identifier of this class of organic boron hardeners lies in the fact that polymeric organoboron compounds are used here, which are used as Substituents on a polymer matrix, which is stable against the ingress of air, boron hydrogen andZ or organobor residues.

These boron-containing radicals are preferably attached to the via B-C bonds Polymer matrix bound. If the boron-containing residues are not the borane residue -BH2 itself represent, are the boron-containing substituents of the Polymermatr S in a further preferred embodiment in turn on boron with at least one further B-C bond bound to one or more organic radicals. Preferred Residues here are hydrocarbon radicals, which, however, also include heteroatoms in particular May contain 0, N, and Z, or S. Suitable substituents on boron are in particular Alkyl, cycloalkyl and Z or aryl radicals which do not pass through in one or in both the polymer matrix occupied valences of boron can be present. Are there any Hydrogen deviating organic radicals in both boron valences, so can they in turn be closed to form a ring system.

Compared to conventional boron alkyl hardeners, the oligomeric or polymer boron compounds have significant advantages. They are not self-igniting and steep, low storage requirements. The activity of this hardener remains in the air even after prolonged storage. The compatibility of the polymerizable component with the hardener can by suitable configuration of the Polymer matrix can easily be ensured for each case. In general, the amount of oligomeric or polymeric material required to harden the monomer component Organoboron compound extremely low.

These polymeric boron compounds can be obtained in a simple thesis are by oligomers or polymers, the addition-ready Kohlensotff double bonds contained, subjected to hydroboration and thereby the boron-containing residues at least.

some of the double bonds ready for addition can be introduced. Both diborane and mono- or disubstituted ones are suitable for the hydroboration Boranes, i.e. compounds of the general mean formula R4R5BH, where in this formula R4 is an organic radical, preferably a hydrocarbon radical, and R5 is hydrogen or also an organic radical which is identical to or different from R4 it can be different or a ring system together with R4 and the boron forms.

The ethylenic double bonds accessible for hydroboration Depending on its structure and molecular weight, the polymer matrix can be flowable with a low viscosity to be firm. Their mean molecular weight can reach values of several million range and is usually in the range of about 150 to 3 million. Lower Values within this range are often preferred, for example those in the Range from about 300 to 500,000, and especially those in the range of about 500 up to 10,000. Here, too, it may be desirable that the polymer matrix and also the polymeric organoboron compounds obtained therefrom are viscous at room temperature are flowable or spreadable.

Here, for example, the molecular weight of the polymer matrix can be in the range from about 300 to 3000 are particularly suitable. For the effectiveness of the invention This is not a prerequisite for the polymeric organoboron compounds used as initiators. On the contrary, the storage stability can be corresponding to that of solid at room temperature polymeric organoboron compounds are particularly good, the polymeric matrix can be the hydroboration can be ethylenically unsaturated to any degree. Preferred are appropriate materials that have an iodine number in the range before hydroboration from about 1 to 500 showing l. Within this range are particularly preferred Values of the iodine number from about 5 to 100 and especially from about 8 to 50.

The ethylenic double bonds accessible to hydroboration can in the starting polymer in the main chain and / or in side chain substituents are present.

The polymer matrix can accordingly be straight-chain or branched Have structure, but are also polymeric materials with a cross-linked structure not excluded.

In principle, all types of polymer are suitable as the polymer matrix, provided that they have double bonds accessible to hydroboration and not reactive ones Have groups that are involved in the introduction of the boron-containing groups into the polymer material lead to undesirable side reactions.

The polymer material can be polymerized or co-polymerized olefinically unsaturated components, by polycondensation or by polyaddition have been made. By in itself.

known suitable selection of the types of monomers making up the polymers becomes the desired content of reactive double bonds for the subsequent hydroboration ensured in the polymer material.

Unsaturated oligomers are particularly suitable as the polymer matrix or polymers obtained by polycondensation. Into consideration all known types of polycondensate such as polyester, polyamides, polyimides, Polycarbonates, polyurethanes and the like. However, oligomers or Types of polymers obtained by polyaddition. The details are the older ones German patent application D 6.461 (P 32 01 731.6) can be found.

The extent of the hydroboration on the polymer matrix can be within the range of the total double bonds present can be freely selected. It has, however Proven to be advantageous if at least a substantial proportion of these double bonds is implemented by introducing the boron-containing substituents. So are in preferred Embodiments of the invention at least 30% and preferably at least 50 % of the ethylene double bonds originally present in the polymer matrix hydroborated. Such polymeric organoboron compounds are particularly suitable, in which at least 80%, preferably at least 90% or even at least 95% of the ethylenic double bonds from the reaction with the boron-containing components have been. A practically completely hydroborated matter; is in many cases the preferred initiator within the meaning of the teaching according to the invention.

In addition to diborane (bs3), organoborane compounds are used for tlydroboration into consideration, the one or two organic radicals, in particular hydrocarbon radicals exhibit. Preferred organic radicals here are alkyl, cycloalkyl and Z or aryl radicals, where two radicals which may be present also with one another - including the Boratoms - can be closed to form a ring. The substituting hydrocarbon radicals in particular each have no more than 25 carbon atoms.

Preferably, each of these radicals contains no more than about 12-15 C atoms.

A particularly suitable one. ases of organoboron compounds for The polymeric initiator components are represented by organoboron monokydridyerbin fertilize, especially dialkyl monokydrides. A typical representative of such boron compounds is also here the 9-borabicyclo [3.3.12 nonane, which is preferred for practical reasons is.

Another interesting class of organoboron initiators is im the following under f): f) In this embodiment, the to be used Organoboron compounds characterized in that they contain hydrogen boron residues or organoboron residues of fatty acid and / or fatty alcohol esters.

These boron alkyl compounds are hydroboration adducts of diborane and / or organoboron compounds with at least one B-H bond to fatty acids and / or Fatty alcohol esters that contain at least a portion of the fatty acid and Z or fatty alcohol residues Contain carbon double bonds ready for addition.

For the nature and manufacture of this class of boron alkyl compounds The following details apply in detail: Esters or, respectively, serving as a matrix Ester mixtures contain hydrogen boron and Zor as substituents via a B-C bond Organobor residue.

If these boron-containing residues do not represent the borane residue-BH2 itself, are these boron-containing substituents for their part in a preferred embodiment on boron with at least one further B-C bond to one or more organic Leftovers bound. Preferred residues here are raw hydrogen residues, but they are even. Heteroatoms, in particular 0, N and Z or S can contain. Suitable nete Substituents on boron are in particular alkyl, cycloalkyl and / or aryl radicals, the in one or in the two valences of boron not occupied by the ester matrix may exist. Are such organic residues other than hydrogen in two boron valences, they can in turn be closed to form a ring system be.

These boron compounds can be obtained in a simple manner by that the s- @@ - matrix starting material containing olefinic double bonds the hydroboration with diborane or preferably with mono- and especially disubstituted Boranes of the general formula R 6R7 BH subject, where in this formula R6 a organic radical, preferably a hydrocarbon radical, and R7 hydrogen or likewise is an organic radical which may be the same as or different from R6, or also forms a ring system together with R6 and the boron. Preferred organic residues are alkyl, cycloalkyl and Z or aryl radicals.

Such hydrocarbon radicals which substitute the boron preferably have each has no more than 25 carbon atoms. In particular, each does not contain these residues Form more than about 12 to 15 carbon atoms in a particularly preferred embodiment R6 and R7 together with the boron atom form a ring system which has the specified numerical values for the number of carbon atoms does not exceed. This can also be done at the beginning said 9-BBN should be preferred for practical reasons.

The ester base serving as a matrix is of decisive importance to. The starting material for this matrix is characterized by the fact that monofunctional Fettsex-en and / or monofunctional fatty alcohols to esters or ester mix are implemented, at least in a proportion of their fatty acid and / or fatty alcohol components Have carbon double bonds ready for addition.

The term “fatty acid” or “fatty alcohol” is included monofunctional components of the type mentioned with a carbon number im Range from about 8 to 32 carbon atoms, preferably in the range from about 14 to 22 carbon atoms. The unsaturated fatty acids or unsaturated fatty alcohols can be synthetic or be of natural origin. It is preferably one or more times olefinically unsaturated alkene monocarboxylic acids or monoalkenols of the specified Carbon number. The carbon chains of these fatty acids or fatty alcohols can be straight-chain and Z or branched.

The counter component forming the particular ester can be a monovalent one or a polyhydric alcohol or a monofunctional or a polyfunctional one Be carboxylic acid. It is possible that carbon double bonds are ready for addition in only one component - i.e. only in the fatty acid or in the fatty alcohol - are present, but both ester-forming components can also be olefinic Contain double bonds. For the preparation of the boron alkyl compounds, at least a substantial proportion of these double bonds are subjected to hydroboration.

In a preferred embodiment, the ester matrix is by esterification a monofunctional component (C acid or alcohol) with a multifunctional component Opposite component (alcohol relational wise wise acid) is formed. Particularly preferred matrix materials can be esters of unsaturated monocarboxylic acids (unsaturated fatty acids) with polyhydric alcohols. As a polyvalent ester-forming Reaction components are, in particular, corresponding compounds of a functionality up to 6, preferably with a functionality of 2 to 4, are suitable. So are in the preferred embodiment as a matrix for the boron-containing substituents monocarboxylic acids of the specified carbon number range with polyhydric alcohols - especially with dihydric alcohols, trivalent or tetravalent alcohols - esterified.

It can be useful that the polyfunctional ester component has a comparatively low number of carbon atoms, for example in the range from 2 to 10, preferably in the range from 2 to 6 carbon atoms. As polyfunctional alcohols are suitable. accordingly especially the lower ones Glycols such as ethylene glycol, propylene glycol-1,2, propylene glycol-1,3, the C4 glycols with terminal and / or internal hydroxyl groups or corresponding ones C5 and C6 connections. Glycerin is also a particularly preferred alcohol or polyhydric alcohols of the pentaerythritol type.

Conversely, monofunctional fatty alcohols with lower polycarboxylic acids in particular lower dicarboxylic acids or lower tricarboxylic acids be esterified.

It is also possible to use synthetic or natural fats and / or as an ester matrix for the subsequent HxTdroboration. Basically the unsaturated esters can be mixed with saturated components for example in a mixture with saturated esters and / or as a mixture of different types unsaturated esters are present.

The ethylenic double bonds accessible for hydroboration Esters or fats and / or oils can, depending on their structure and molecular weight low viscosity, flowable to solid.

The unsaturated esters or ester mixtures such as fats and oils and the like can be ethylenic to any desired extent prior to hydroboration be unsaturated. Corresponding starting materials which have an iodine number are preferred to about 280, preferably in the range from about 1 to 205. Inside this In the range, values of the iodine number from about 5 to 130 are particularly preferred.

The extent of the hydroboration on the ester matrix can be within the scope of total double bonds present can be chosen freely. It has, however Proven to be advantageous if at least a substantial proportion of these double bonds is implemented by introducing the boron-containing substituents. So are in preferred Embodiments more than 30%, preferably at least 50% and in particular at least about 70% of the ethylenic double bonds originally present in the ester matrix hydroborated. Organoboron compounds in which -related are particularly suitable on the reaction batch - at least 80%, preferably at least 90% or even at least 95% of the ethylenic double bonds of the conversion tongue have been supplied with the boron-containing components.

The unsaturated esters are used for hydroboration under perfect conditions Exclusion of oxygen implemented by reaction with the selected borohydride compounds. It is expedient to work in solvents. The known ones are suitable Solvent for organoboron compounds, especially tetrahydrofuran, glycol or Polsfother such as diethylene glycol dimethyl ether, but also esters, hydrogen halides and the same. The reaction is expediently carried out in the temperature range from about 0 to 1000 C, especially in the range from about room temperature to 700 C.

Further details of the invention The binder systems according to the invention from polymerizable component (A) and hardener or initiator component (B) can be designed as two-component formulations. For practical use can then the adhesive component (A) with the hardener component (B) before application be mixed on the parts to be bonded. The open time of the glue s The requirements are met by matching the amounts of components (A) and (B) customized.

The processing of the binder systems according to the invention is, however also according to the type of "no-mix adhesives" or "acrylate adhesives of the second or

third generation "possible (cf. on this' adhesive eye = 1976, 21-24 and "AdhÇion", 1981, 156-161).

Here, the separate mixing of the adhesive component and the hardener component can be dispensed with.

Rather, the initiator component is initially applied in a thin layer applied to one or both of the surfaces to be bonded, then the adhesive component applied. The gluing is done by fixing the parts in the desired Position.

The organoboron compounds listed above under a) to f) can find use as a primer phase or be used therein. Special The organoboron systems described under d) to f) are important in this context to.

In this context in particular, a hardener system can be important to come, which is described in the earlier German patent application D 6391 (P 31 43 945.4) and can be produced as follows: g) In a first process stage polymerizable monomers with ethylenic double bonds to the exclusion of Oxygen is polymerized by adding organoboron compounds. After reaching The thickening required for processing is carried out by this polymerization Addition of an anionic inhibitor canceled.

One makes use of the fact, known from the literature, that Organoboron compounds not only according to a radical mechanism - with access of oxygen - that trigger polymerization that rather in the absence of Oxygen ethylenically unsaturated monomers even after a slow expiration anionic mechanism can be polymerized by organoboron compounds, This comparatively slow reaction step leads to a gradual one Thickening an initially easily mobile monomer phase the influence of the organoboron compounds. Is the sufficient thickening through polymer formation occurs, the anionic polymerization can be terminated. Also here lies then ultimately as hardener component B a mixture of organoboron compounds and polymer components.

The ethylenically unsaturated monomers here are derivatives of acrylic acid undZo 1ethacrylic acid is particularly suitable, in particular corresponding esters with monofunctional ones or polyfunctional alcohols and corresponding acid amides, which are on the Amidstiackstoff substituted in a manner known per se, for example with hydrocarbon radicals could be.

With regard to the organoboron compounds to be used, the above apply general information provided.

As inhibitors or stabilizers against anionic polymerization all the compounds are well suited that are also used to stabilize cyanoacrylic acid esters are useful, for example acidic components such as phosphoric acid, boric acid, boric acid esters and the like, sulfonic acids or sultones.

Particularly suitable inhibitors, however, are carboxylic acids with free Carboxyl group. The use of olefinically unsaturated ones has proven to be expedient Carboxylic acids, on the one hand with organoborohydride compounds via their double bond are reactive, but on the other hand also via this double bond in a Pol, Inerisatlonsreaktion can thus ultimately become an active component of the adhesive. Particularly suitable as Inhibitors against anionic polymerization are accordingly Acrylic acid and / or methacrylic acid.

Your free carboxyl group not only brings the anionic one The polymerization process comes to a standstill, the free carboxyl groups in the adhesive system their adhesion-improving effect in a manner known per se.

Finally, according to the invention, it is possible to use one-component adhesive systems to use, which according to the teaching of the European patent application 0 051 796 (D 6246 EP) are built up, but those mentioned at the outset as the polymerizable component Contain absorbable (meth) acrylate compounds.

a) Quantity ratio of hardener to adhesive components for hardening the reaction masses according to the invention are based on the polymers described Boron initiators about 0.1 to 40 percent by weight, in particular about 0.1 to 30 percent by weight - each based on the portion to be polymerized - a. Preferred are the polymeric hardener in amounts of about 0.5 to 30 percent by weight - based on the portion to be polymerized - used.

b) Concomitantly used polymers often contain the polymerizable Masses of prefabricated polymers in addition to the polymerizable components such as polymethyl (meth) acrylate, copolymers of methyl (meth) acrylate, Polychloroprene, chlorosulfonated polyethylene, nitrile rubbers and urethanes for reinforcement respectively Elastification and at the same time as a thickener. To ensure the degradability of the To ensure hardened systems are polyhydroxycarboxylic acids, such as Polyglycolic acid and polylactic acid, particularly suitable. This will make the processing the masses, such as the adhesive, equal tert. In detail, the apply Information on the relevant state of the art.

In many cases it is useful or necessary to use additional auxiliaries such as fillers, for example quartz flour or the like, to be added. In the end it may be useful to color with suitable dyes or pigments.

c) Comonomers to be used as additional polymerizable constituents the numerous known compounds can be used in the plastic compositions according to the invention with polymerizable ethylenic double bond are used, the customary in, for example, casting resins, fillers and especially in reactive adhesives come to use. Accordingly, the esters of are particularly suitable Acrylic acid and / or d-substituted acrylic acids, such as methacrylic acid - hereinafter referred to as (meth) acrylic acid compounds -with monovalent or polyvalent especially dihydric alcohols. However, other known derivatives are also suitable the (meth) acrylic acid, in particular the corresponding acid amides, which are attached to the amide nitrogen also, for example, with hydrocarbon residues be established can. Further possible substituents in the position of the (meth) acrylic acid derivatives are, for example, halogen, in particular chlorine and / or bromine, cyano or in general Alkyl radicals with up to 10 carbon atoms.

Examples of (meth) acrylic acid esters of monovalent alcohols are called: (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, Ethylhexyl (meth) acrylic acid.

Examples of corresponding esters with polyvalent alcohols are such with ethylene glycol, diethylene glycol, polyethylene glycol and trimethylolpropane, di- and Mono- (meth) -acrylic acid esters of glycerol, di (meth) -acrylic acid esters of tri- and Tetraethylene glycol, from di-, tri-, tetra- and pentapropylene glycol, the di (meth) acrylic acid esters of ethoxylated or propoxylated diphenylol propane. (Steth) acrylic acid esters are also available of alcohols in question, which are derived from dihydroxymethyltricyclodecane or including those that have been produced on the basis of tricyclodecane, with two alcoholic functions in the ring system through reaction with dicarboxylic acids such as maleic acid or cyclohexanedicarboxylic acid or terephthalic acid are extended.

Reaction products of diglycidyl ether can also be used of diphenylolpropane with methacrylic acid and / or acrylic acid. Also are reaction products of diisocyanates or triisocyanates, for example tolylene diisocyanate, diphenylmethane diisocyanate, Isophorone diisocyanate, trimerized Tolylene isocyanate and the like useful with hydroxyalkyl (meth) acrylates as polymerizable ingredients.

However, polymerizable monomers such as vinyl acetate, Vinyl halides, for example vinyl chloride, vinyl bromide or vinyl fluoride, styrene, Diphenylbenzene, crotonic acid and maleic acid esters or the so-called, optionally styrenated unsaturated polythene gels. These last mentioned connections are generally only in minor amounts in reactive adhesives, for example used in amounts of up to 25 percent by weight of the polymerizable constituents.

In addition, 2-acryloyloxyethyl phosphate, 2-methacryloyloxyethyl phosphate, Bis-2-acryloyloxyethyl phosphate, bis-2-methacryloyloxyethyl phosphate, tris-2-acryloyloxyethyl phosphate, Tris-2-methacryloyloxyethyl phosphate and acid amides such as dimethylene bis (meth) acrylamide, Tetramethylene bis (meth) acrylamide, trimethylhexamethylene bis (meth) acrylamide, tri (meth) acryloyldiethylenetriamine and the like.

Examples of test specimens (see G. Giebel et al., Biomed. Techn.

26, 170, (1981)) Bone test bodies from bovine cortalis with the dimensions 50 x 20 x 5 mm were placed in the middle - exactly at right angles to the side surfaces (50 x 5 mm) - osteotomized with a diamond cutting saw while rinsing with water.

In this way, precisely fitting parts to be joined with a 2 contact surface were created made of 1 cm.

Test body pre-treatment (see Giebel et al., Op. Cit.) The no further Pretreated bone test specimens were immersed in a 370 C warm Ringer's solution for 2 hours placed to intensively wet the bones.

Bonding a) 2-component adhesives Adhesive resin (A) and hardener (B) are used mixed.

The mixture is applied to the damp bone.

b) No-mix adhesives Only the hardener (A) is applied in a thin layer Applied to both surfaces to be glued.

The adhesive resin (B) is applied directly to the connection.

The test specimens are joined, transferred to a press made of PVC and loaded with 5 N. The glue press prevents the test specimen from shifting to the side during curing.

Hardening conditions (see Giebel et al. Loc. Cit.) The joined bones are in the glue press for 20 minutes in a climatic chamber at 370 C and approx.

Stored at 100% relative humidity. Then they will removed from the glue press and stored in Ringer's solution at 370 ° C. for 20 hours.

Strength measurement The tensile strength is measured on a universal testing machine torn at a feed rate of 12 mm / min.

Due to the wide control given by the natural substrate of the measured values, the strength ranges from 6 individual tests were given.

Resin component A Examples -1 to 6 Oligohydroxycarboxylic acids with hydroxyl end groups a) Representation from glycolic acid and ethylene glycol in a three-necked flask with a stirrer and distillation bridge, glycolic acid and ethylene glycol are presented. Under nitrogen quickly gets to 1500C and then tm the course of 6 hours of 150 heated to 2000 C. The largest part of the water of reaction already splits, which indicates the conversion of the ester condensation, from. The approach is allowed to be around 1500 Cool to C, evacuate carefully to 10 Torr and complete the conversion at 2000C and 10 Torr. After 30 minutes, the product is heated to approx.

Bottled at 1500 C. The composition of the batches and the oligomer properties are shown in Table 1 (Examples 1 to 3). Table 1 Oligohydroxycarboxylic acids with hydroxyl end groups from glycolic acid and ethylene glycol Example educts, reaction, acidity, calculated nature Glycolic acid ethylene glycol water number molecular weight mol mol% d. Th. G / mol 1 3 1 100 14 252 clear, viscous, light yellow 2 4 1> 90 20 294 viscous, white 3 6 1> 98 24 410 waxy, white b) Preparation from ethyl lactate and ethylene glycol In a three-necked flask with stirrer and distillation bridge, ethyl lactate and ethylene glycol are combined. 70 ml of 0.2% strength methanolic sodium methylate solution are added as a catalyst and the batch is then heated to 1500.degree. The temperature is carefully increased further up to 1800C, so that about 800C ethanol is constantly distilled off. When the splitting off of ethanol has ended after about 16 hours, the mixture is evacuated to 10 Torr at a bath temperature of 1500 ° C. and the substance is then bottled under nitrogen. The composition of the batches and the oligomer properties are shown in Table 2 (Examples 4 to 6). Table 2 Oligohydroxycarboxylic acids with hydroxyl end groups from ethyl lactate and ethylene glycol Example products P roducts Lactic acid ethylene ester ethylene glycol Yield Molecular Weight Nature mol mol of ethanol % clear, viscous, @ 2 1 95 193 (osmosis) orange colored 5 4 1 92 clear, viscous, Brown 6 6 1 96 clear, viscous, red-brown EXAMPLES 7 to 10 Olihydroxycarboxylic acids with carboxyl end groups General instructions a) By reacting hydroxyl-terminated oligohydroxycarboxylic acids with succinic anhydride , Reflux condenser and nitrogen inlet combined and stirred for 8 hours at 800 C under nitrogen. The product is characterized by the following key figures: Acid number: 296 OH number: b) Preparation from glycolic acid and adipic acid In a three-necked flask with stirrer and distillation bridge, dicaronic acid and hydroxycarboxylic acid are placed. It is heated quickly to 1500 ° C. under nitrogen and then from 150 to 2000 ° C. in the course of 6 hours. Most of the water of reaction, which shows the conversion of the ester condensation, splits off. The batch is allowed to cool to about 1500 ° C., carefully evacuated to 10 torr and the conversion is completed at 2000 ° C. and 10 torr. The product is bottled hot under nitrogen ) refer to.

Table 3 Oligohydroxycarboxylic acids with carboxyl end groups from glycolic acid and adipic acid Example products P roducts Glycolic Acid Adipic Acid Yield Acid Number Molecular Weight Nature mol mol reaction from acid water number % g mol-1 8 1 1> 99 620 181 waxy, fixed 9 3 1> 98 376 298 waxy, soft 10 4 1> 96 334 336 waxy, soft EXAMPLES 11 to 20 Ollgo'hydro'xy'c'arboxylic acids with polymerizable end groups a) Oligohydroxycarboxylic acids with polymerizable end groups from oligohydroxycarboxylic acids with terminal hydroxyl groups In a three-necked flask with a stirrer and water separator, the oligohydroxycarboxylic acids and 1.1 equivalent methacrylic acids with hydroxyl end groups are obtained submitted. At the same time - based on methacrylic acid - equal parts by weight of toluene and 2 percent by weight each of p-toluenesulfonic acid and hydroquinone are added.

The mixture is brought to the boil with rapid stirring and that The water of reaction formed is separated off on the water separator.

If less than 90 to 95 percent by weight after a reaction time of 5 hours of the theoretically expected water of reaction have split off, are again 20% of the originally added amount of methacrylic acid with 2 percent by weight each para-toluenesulfonic acid and hydroquinone were added and the reaction continued.

The reaction is complete as soon as 90 to 95% of the expected value is reached Have formed water of reaction. The reaction product is after cooling in given twice the volume of ethanol and filtered. The clear ethanolic solution if you concentrate on a rotary evaporator to 1/4 of the original volume, it pours in the same amount of water and neutralize it with sodium hydrogen carbonate. The organic phase is separated off and the aqueous phase is extracted with toluene the organic phases are combined, washed three times with water and over sodium sulfa dried. The solvent is first used at room temperature on a rotary evaporator, then deducted at 10 4 torr. The composition of the approaches and the properties the polymerizable oligomers are listed in Table 4 (Examples 11 to 16).

Table 4 Oligohydroxycarboxylic acids with polymerizable end groups Educt Yield Nature Example diol from example reaction water % 11 1> 97 homogeneous, thin-bodied, Brown 12 2> 95 homogeneous, thin-bodied, Brown 13 3> 95 homogeneous, thin-bodied, Brown 14 4> 95 homogeneous, thin-bodied, Brown 15 5> 95 homogeneous, viscous, Brown 16 6> 90 homogeneous, viscous, Brown b) Oligohydroxycarboxylic acids with polymerizable end groups from oligohydroxycarboxylic acids with terminal carboxyl groups The oligohydroxycarboxylic acid with terminal carboxyl groups is placed in a three-necked flask with stirrer and reflux condenser and 1.0 equivalent of glycidyl methacrylate with 0.1 percent by weight of benzyltrimethoxydylammonium is added. The mixture is heated to 80 ° C. over a period of 45 minutes while stirring, and the reaction is continued at 80 ° C. until the acid number has fallen below 35. The reaction is usually over after 10 to 20 hours.

The composition of the approaches and the properties of the polymerizable Oligomers are listed in Table 5 (Examples 17 to 20).

Table 5 Oligohydroxycarboxylic acids with polymerizable end groups Example educt product Dicarboxylic acid from example Acid number Nature 17 7 24 homogeneous, viscous, yellow 18 8 30 homogeneous, viscous, light- yellow 19 9 34 homogeneous, highly viscous, light yellow 20 10 31 homogeneous, highly viscous, light yellow Initiator components B Initiator component B 1 4 mol of trimethyladipic acid and 5 mol of hexamethylene glycol are placed in a three-necked flask equipped with a stirrer and distillation bridge. It is heated quickly to 1500 ° C. under nitrogen and then from 150 to 2000 ° C. in the course of 6 hours. The largest proportion of the reaction water, which shows the conversion of the ester condensation, is already split off. The batch is allowed to cool to about 1500 ° C., carefully evacuated to 10 torr and the conversion is completed at 2000 ° C. and 10 torr. The oligoester is bottled hot. It is viscous and brown in color.

To remove residual oxygen, 100 g of the oligoester are mixed in 100 g of freshly distilled tetrahydrofuran dissolved. Then the solvent stripped in vacuo at 10-4 torr. 100 g of the oligoester are added to a glove box 100 g of distilled, degassed THF were again added and poured into this solution under complete Oxygen exclusion 41 g of 9-borabicyclo [3.3.1] nonane entered. The mixture will stirred for further homogenization. The mixture is then heated for 1 hour while stirring to 600 ° C. The THF is drawn off in vacuo and the storage vessel is closed. the Samples are taken under protective gas and with complete exclusion of oxygen. The product is a viscous, dark brown liquid.

Initiator component B 2 5.0 g of 9-BBN are under vol constant exclusion of oxygen presented in a 250ml flask. In this flask in a high vacuum, (10 4 Torr) 100 g recondensed dry, freshly distilled methyl methacrylate. The flask is capped and shaken until the 9-BBN has gone into solution. After 2 days the mixture shows a significantly increased viscosity. It will then - also with complete exclusion of oxygen - 0.5 g oxygen-free, under Argon distilled methacrylic acid and 5.0 g 9-BBN were added. This mix is Storage-stable without any further increase in viscosity.

Initiator components 3 3 to B 4 To remove residual oxygen, the fats, oils or fatty acid derivatives listed in Table 6 are dissolved in the same amount of THF. The solvent is then stripped off in vacuo at 10 4 Torr. Equal parts by weight of frisk-distilled, degassed THF are again added to a glove box and the fats, oils or fatty acid derivatives are dissolved. With complete exclusion of oxygen, the amounts of 9-borabicyclo [3.3.i nonane (9-BBN) listed in Table 6 are added and the mixture is stirred until the 9-BBN has dissolved quantitatively. The mixture is then heated to 600 ° C. for 1 hour with stirring. The THF is stripped off in vacuo and the storage vessel is closed. Samples are taken under protective gas and with complete exclusion of oxygen, Table 6 shows the initiator components B 3 - B 4 No. Oil, fat, fat- iodine- amount used degree of modification product-own- acid derivative number 9-BBN / g per 100 g of double bonds Noun B 3 oleic acid methyl- 85.8 41 100 homogeneous, low- ester 1) viscous, gleb B 4 linseed oil 178 86 100 homogeneous, viscous, light yellow 1) The conversion of the reaction was determined using the 'H-NMR spectrum | | (-CH = CH resonance at = 5.3 ppm) and the 13C-NMR spectrum (-CH = CH resonances at = 129.5 and 129.8 ppm).

The conversion at the double bond is in Example B 3 70 # 5%.

Results Selected monomers were mixed with 5 percent by weight of a mixture of methacryloyloxyethyl phosphate and bismethacryloyloxyethyl phosphate and used as resin component (A). When bonding bone material under simulated in vivo conditions, "the following tensile strengths were achieved with the specified hardeners (B) (1 to 3 percent by weight in each case) (Table 7). Table 7 Overview of the measured tensile strengths / Ncm-2 Resin component, hardener component B AB 1 (2K) B 2 (no-mix) B 3 (2K) B 4 (2K) Example 12 430-1070 90-140 Example 260-660 150-550 240-410 Example 18 180 - 400 180 - 330 90 - 200 130 - 200

Claims (16)

Claims 1. Suitable for gluing the body's own hard tissue Surgical agent system based on a polymerizable (meth) acrylate adhesive. and a polymerization initiator, characterized in that it is used as absorbable (meth) acrylate component liquid to solid (meth) at room temperature -acrylic acid esters with (meth) -acrylate residues on polyester oligomer chains from hydroxycarboxylic acids and contains organoboron compounds as starters. 2. Binder according to claim 1, characterized in that the absorbable (.Meth) acrylate component at least partially more than one (meth) acrylate residue - preferably 2 (meth) acrylate radicals - on the hydroxycarboxylic acid polyester oligomers having. 3. Binder after. Claims 1 and 2, characterized in that some of the (meth) acrylate radicals are terminally attached to the polyester oligomers are present, preferably 2 (meth) acrylate radicals are provided in the i, £ -position. 4. Binder according to Claims 1 to 3, characterized in that the polyester oligomers are formed from monohydroxy monocarboxylic acids, which are preferably 2 to 10, in particular 2 to 6, carbon atoms. 5. Binder according to Claims 1 to 4, characterized in that the polyester oligomers made from glycolic acid, lactic acid, hydroxypropionic acid, and hydroxybutyric acid and / or hydroxybenzoic acid are built up. 6. Binder according to Claims 1 to 5, characterized in that the polyester oligomers & in average molecular weight in the range of about 200 to 600, preferably in the range of about 300 to 500, have. 7. Binder according to Claims 1 to 6, characterized in that the polyester oligomers with the concomitant use of monofunctional and / or preferably difunctional alcohols or carboxylic acids or carboxylic acid anhydrides and / or produced with the use of primary, secondary and / or tertiary monoamines have been. 8. Binder according to Claims 1 to 7, characterized in that any monofunctional used in the preparation of the polyester oligomers Components in amounts not exceeding 95 mole percent, preferably not more than 50 mole percent, and in particular in amounts not exceeding 10 mol percent - in each case based on the mixture the monofunctional components and the dialcohols or dicarboxylic acids - used have been. 9. Binder according to Claims 1 to 8, characterized in that the resorbable (meth) acrylate components flow to pasty at raw temperature are spreadable and preferably have a viscosity in the range at room temperature from about 500 to 70,000 mPas 10. Binder according to claims 1 to 9, characterized in that they contain organoboron compounds as starters, the have practically no spontaneous combustion in air, but at the same time at body temperature are capable of initiating polymerization when exposed to air. 11. Binder according to Claims 1 to 10, characterized in that that they are organoboron compounds containing alkyl and / or aryl radicals as starters which can also have B-H bonds. 12. Binder according to Claims 1 to 11, characterized in that that they use at least one boron trialkyl compound and Z or at least one as a starter Boron alkyl hydride compound - in this case in particular a dialkyl borohydride - contain. 13. Binder according to Claims 1 to 12, characterized in that that they exist as 2-component systems, the components of which are polymerizable Component (A) and starter-containing component (B) - when used together mixed or processed using the no-mix method. 14. Binder according to Claims 1 to 13, characterized in that that at least one of the following systems is present as starter component (B): a) a homogeneous mixture of at least one organoboron compound which can be activated by admission of air with at least one liquid to solid at room temperature, preferably with the Component (A) compatible, the organoboron compounds with respect to inert organic Oligomers or polymers; b) polymeric organoboron compounds acting as substituents on a polymer matrix, which is stable against the ingress of air, boron hydrogen and / or organobor residues exhibit; c) Boron alkyl compounds, the boron hydrogen residues and / or organoboron residues of fatty acid and / or fatty alcohol esters. 15. Binder according to claim 14, characterized. marked that the Oligomers or polymers according to a) a polymer based on derivatives - preferably Esters and Z or optionally substituted acid amides - of (meth) acrylic acid is, in particular with the exclusion of oxygen in situ under the influence of the Organoboron compounds have been made from its monomers. 16. Use of the binder systems according to claims 1 to 15 for in-situ production of resorbable molded parts when gluing endogenous parts Hard tissue optionally together with plastic and / or metal.