DE1928104B2 - - Google Patents

Description

temperature - which leaves enough time to put it in the mouth

ao cave to be brought in and processed there before the polymerization occurs. The low viscosity

Alkoxyalkyl-2-cyanoacrylates are known and these compounds contribute to the formation of stronger compounds

already used for adhesives (including bonds to the tooth surfaces, since the liquid

U.S. Patent 2,784,215). Monomers even in the smallest depressions and

The invention relates to fluoroalkoxyalkyl infiltration cracks or crevices.

2-cyanoacrylates of the general formula The viscosity of the composition can optionally by

_CN dissolving polymeric substances, such as 5% polymethyl meth-

/ X acrylate. For certain uses

CH ₂ = C _x purposes e.g. B. for temporary fillings can

^x CO - CH -CH —OCH —CF ₃ 3 ° finely divided inorganic fillers are added,

: ii ³ to the abrasion resistance and the strength of the filling

to increase λ and improve its aesthetic appearance.

in which X is —H or —CF ₃ . The adhesive bonds formed by poly- In the field of prosthetic dentistry merization of these fluoroalkoxyalkyl-2-cyanoacrylates, the compounds according to the invention are formed and in the analogous, non-fluorine-containing 2-cyanoacrylates used by haft as general adhesives or binders usual way applied. In the ten bonds a surprisingly greatly improved area of restorative or conservative strength and durability in the presence of water Dentistry are the compounds according to the invention. The fast-polymerizing compounds 40 gene-containing compositions are particularly useful as found primarily in dentistry, e.g. B. as part of temporary fillings. The temporary filling of partial dentures, bridges, braces must seal the cavity effectively against the teeth, for endodontic fillings under oral cavity secretions and must not irritate the pulp. Use of substitute materials for lining. The compounds according to the invention or underfilling of cavities before the insertion of the 45 result, mixed with about 70 ⁿ _o silane-coated cast fillings, for coating pin teeth or lithium aluminum silicate, a temporary filling material crowns and as a paint for preventive coating rial that meets these requirements well and that of tooth areas sensitive to caries. in the same or similar way as the plastic

Up to now used in dentistry for filling the jaw.

orthopedics, for prostheses and root fillings. The compounds according to the invention are also well used. Adhesives and sealants are not fully satisfactory for use in endodontic fillers because they often pass through the oral cavity when the pulp chamber is cleaned and its secretions are attacked and so on at which the tooth becomes infected, before the tip of the tooth root is sealed, adhesive interface will form sites of which will. Endodontic sealants must form a permanent seal from caries (Skinner et al., Science 55, and must be non-toxic of Dental Materials, 6th Edition, Chapter 29 [1967]). act on the periapical tissue.
In addition, there are numerous adhesives currently in use. These substances are preferably radiopaque and sealants are corrosive to tooth enamel and are casual. A mass, which consists essentially of an invented-exerting a toxic interaction with the pulp, the compound according to the invention and about 50% barium. In addition, their production is often time-consuming. If sulfate exists, it has the required properties and its use is cumbersome and difficult. In addition, the low viscosity of the Mono-So is z. B. Methyl-2-cyanoacrylate as basic compo- mers and its affinity for the tooth material a component for dental adhesives and sealing compounds highly effective penetration of the polymer into the already known (Owinnett, et al., British Dental cavities of the tooth. This becomes an effective journal , Volume 119, pp. 77 to 80 t1965], and Cue 10 6 $ occlusion of the tooth root apex and other secun et al., Journal of the American Dental Association, the canals caused by the pulp in the reverse band 75 , Pp. 121 to 128 [1967]). When it is used, the tissues
however, various problems were encountered. One of the The resistance of the hardened or poly-

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Compounds according to the invention compared to bonds exposed to aqueous liquids predict the penetration of water-soluble substances. These soon lose their firmness, including the potentially toxic components. Except as adhesives or adhesives, the invention parts can be found It makes plastic oilings particularly suitable for use in other areas as well effective and suitable as underfills for cavities. They polymerize easily to the additionsten. The invented fluoroalkoxyalkyl-2-cyano-like polymers and copolymers ^ as Acrylates not only adhere exceptionally firmly to the film, as well as thermoplastically and at temperatures Tooth substance, they also adhere very well to the deformable well below their decomposition temperature, common commercially available dentures such as The polymerization is carried out by weakly basic Amalgam, so that it is used to firmly bond the filler to substances and to release material through atmospheric moisture with the tooth substance are well suited. dissolves The rate of polymerization can be Control resistance to penetration by varying the amount and additives that of foreign substances are added along the crevices of a certain mass, e.g. B. human Fillings attached to the incisors, organic fillers and polymerization inhibitors has been proven by keeping teeth 15 or 15 stabilizers such as sulfur dioxide, nitric oxide, in a 0.12% aqueous methylene boron trifluoride kept at 37 ° C. and other acidic substances such as water blue solution were laid. It was found that the quinone, 4-methoxyphenol, nitrohydroquinone, penetrated Brenz along the crevices with an underfill catechin and 4-ethoxyphenol.

with 2- (2,2,2-trifluoroethoxy) -ethyl-2-cyanoacrylate very On the other hand, polymerization can also accelerate

was much lower than with a tooth filling without sub- ao niger such as amines or alcohols are added, filling or a commercially available one if faster curing is desired. Underfill substance. Of course, other additives can be added

The sealant preferably contains the will, such as thickeners, plasticizers, to the Fluoroalkoxyalkyl-2-cyanoacrylate combined with a usability of the monomer and its storage filler, e.g. 50% silane-coated lithium aluminum to improve resistance.

mini silicate. A process for producing very pure (95%

Due to the außergewönnlichen strength and or more) fluoroalkoxyalkyl-2-cyanoacrylates is resistance to destruction of the bonds, which is that one of formaldehyde with an ester of cyanoacrylates 2-alkyl-between ^r7 luoralkoxya! And corresponding cyanoacetic acid formed in the presence of a composite dental materials As a mixture of an acid and the addition of an acid, the compounds are highly suitable for use as coatings or feedstocks for dental fillings. Any salts of a primary or secondary, which are either alkylamine and any free acids from the surrounding oral cavity, must be protected or, after completion, only components of the mixture are used and can be polished with difficulty. Exposure to such a coating that it offers the required coating with the appropriate additives below provides the pH value specified in more detail. The resulting protection for the tooth filling and a resin-like surface on the 2-cyanoacrylate polymer then form a thermal surface that can be polished and depolymerized to the desired monomers. staining or staining is very resistant. The thermal depolymerization can be carried out according to the The compounds according to the invention can also * o in the USA patents 2,784,215, 2,721,858 and as comonomer mixtures and as a mixture with 2,763,677 and in the following smaller amounts (ie less than 50 mol percent) Examples of procedures carried out other 2-cyanoacrylates with compatible properties. For the preparation of the above polymers are th, ζ. B. unsubstituted alkyl and alkoxyalkyl, the 2-cyanoacrylates and fluoroalkyl-2-cyanoacrylates corresponding to the desired cyanoacrylates used 45 cyanoacetates, z. B. 2- (2,2,2-trifluoroethoxy) - be set. ethyl 2-cyanoacetate for the production of 2- (2,2,2-tri-

In the majority of uses fiuoräthoxy) -äthyl-2-cyanoacrylate. The cyanoacetic acid options Polymerization is the ester of the invention with formaldehyde or one of its polymers Monomers with small amounts of moisturizing agents, e. B. implemented paraformaldehyde. The presence water on the surface of the parts to be bonded 50 should be avoided, and therefore causes. So a drop of the monomer on the are aqueous formaldehyde solutions, z. B. formalin, Surface one of two to be joined glass or not usable. The reaction medium can be any Metal parts and the other part in contact can be any inert organic solvent that be brought with it. The parts will form an azeotropic mixture in contact with water, e.g. B. benzene held together until the polymerization far 55 or toluene. All the stages of synthesis are under advanced enough. A strong bond forms when carried out under acidic conditions soon look through polymerization. The moisture The mentioned required pH-value for the health The atmosphere is sufficient to mix the polymerization of acid and acid addition salt of a primary catalyze. During and after polymerizing or secondary alkylamine, as »corrected Exceptionally small fluctuations in volume occur notices on. will.

Are adhesions formed in this way during the exact amounts of amine acid salt and free If exposed to aqueous liquids for a longer period of time, the acid for the condensation stage is 25 cm * keep their good binding strength and stability in water, and the pH value of the solution is maintained. at. measure up. If the pH is 5 or below, so

These results could not be based on the ⁵ catalyzes the condensation in adequate results with corresponding non-fluorinated ter ways. If the mixture is water-soluble, this is the alkoxyalkyl-2-cyanoacrylate obtained and the "corrected pH value" at the same time. Mixtures that are not easy

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If

Containing water soluble organic acids can be distilled in packed column. Excess 2,2,2-tri-

25 cm "of an ethanol-water mixture can be dissolved; fluoroethanol was recovered as well as sine at 71

however, the measured pH must then be such as from to 81 ° C / 36 to 85 Torr passing fraction, which from

Gutbezhl et al. in Journal of the American 91% reaction product and 9% 2,2,2-trifluoroethanol

Chemical Society, Vol. 75, S, 565 (1953), 5 was composed.

* ° sWhere that? SninsaJz and the free acid are ² · ^ A ^ trifluoroethoxy-ethyl-cyanoacetate

always present. Glacial acetic acid is preferred, or 85.1 g of cyanoacetic acid (1.0 mol) was used with 192.5 g

strong mineral acids such as hydrochloric acid or sulfuric acid. 2- (2,2,2-Trifluorätboxy) ethanol (1.25 mol) esterified,

The amount of mixture used is not critical in that the mixture of the two reactants is in

and can fluctuate. Usually 300 cm * of benzene to which 0.25 g of p-toluenesulfonic acid is added

Amounts of 0.5 to 1.0 percent by weight, based on sets, was heated. As soon as there is no water

the weight of the cyanoacetic acid ester. parting more in a Dean-Stark trap, that became

Apart from the use of the mixture of benzene solution filtered off and fan vacuum concentrated.

The amine salt and free acid cause the condensation of the 15 By distillation of the residue, the cyanogen

Cyanoacetic acid esters with formaldehyde and the an- acetic acid esters obtained, bp. 98 to 102 ° C / 0.1 to

final depolymerization analogous to that in the Lite- 0.2 Torr,
procedure described (USA.-

Patents 2,721,858 and 2,763,677). Calculated for C ₇ H ₈ F ₃ NO ₃ C 39.8, H 3.8%;

The found in the preparation of the desired fluorine 20 C 39.5, H 3.8%.

alkoxyaIkyl-2-cyanoacrylates used cyanoacetic ". , "" "_ .., _, ^ ~,, ^,

Acid esters easily become ³ · 2- (2,2,2-fluorathoxy) -ethyl-2-cyanoacrylate by direct esterification

of cyanoacetic acid in the presence of an acid such as a mixture of 422.4 g of 2- (2,2,2-trifluoroethoxy) sulfuric acid with one of the two alcohols, ethyl cyanoacetate (2.0 mol), 78 g of powdered ParaFormel 35 formaldehyde (2.6 moles), 2.5 g piperidine hydrochloride

X and 1 cm ^{3 of} glacial acetic acid in 800 cm ^{3 of} benzene was under

I heated to reflux until no more water separated out.

j-IO (CH ₂₎ 2 ₃ OCHCF D ^ ^e resulting solution was diluted with 400 cm ³ of acetone, filtered, combined with 210 g of tricresyl phosphate

in which X has the meaning given above, inherit. 30 and by distilling under reduced pressure

These alcohols are known. constricted. The viscous residue was 10 g

Polyphosphoric acid and 0.5 g of pyrogallol added and

Example the depolymerization by heating this mixture

under reduced pressure with the introduction of a

1. 2- (2,2,2-Trifluoroethoxy) ethanol 35 strong sulfur dioxide stream and under rapid,

mechanical stirring causes. The raw monomer

In a 1 liter round bottom flask with a mechanical yield of 310 g, it was cooled in a dry ice

A stirrer and two dry ice condensers were collected 340 g th initial charge; it went at 185 to 195 ° C /

2,2,2-trifluoroethanol (3.4 mol), 3.4 g sodium hy-0.15 torr over. Little by redistillation

Submitted droxide and 3.4 cm ^{3 of} water. The mixture 40 phosphorus pentoxide in the presence of sulfur dioxide

was heated to 70 ^° C. and stirred. About 100 g of a 99% pure monomeric product was obtained,

Ethylene oxide (2.27 mol) were in the course of bp 86 ° C / 0.2 Torr.

3.5 hours into the upper end of a condenser. In an analogous manner, starting from

and condense into the reaction mixture 1,1,1,3,3,3-hexafluoroisopropanol 2- (l, l, l, 3,3,3-hexa-

calmly. The mixture was prepared for a further 4 hours at 45 fluoroisopropoxy) ethyl cyanoacrylate, bp 123

Stirred 70 ° C and through a with glass spirals up to 5 ° C / 2 Torr.

Claims (5)

1 2 The main problem is the easy decomposition by the Claims: Moisture of the oral cavity and the high polymer satjonsgeschwujdigkeit, which makes the application difficult I. FluonUkoxyalkyW ^ anacrylste of the formula In addition, the methyl-2-cyanoacrylate acts in un- 5 Desirably toxic to the tissue (Archives of / CN _χ Surgery, Volume 94, pp. 153 to 156 [1967], and Journal CH, = C ^ π of Biomedical Materials Research, Volume 1, pp. 3 to 9 ^ rn - rrr - rv! —Nru - rp [1967]) · Adhesive coatings and / or sealing cu CH, cn, ucH ci-j masses which the fluoroalkoxyalkyl according to the invention "ίο contain 2-cyanoacrylates, on the other hand, cause bonds, ⁰ which are unusually strong and extremely durable in which X stands for —H or —CF ₃ is opposed to the decomposing effect of moisture in the mouth and has no adverse effect 2. Use the compounds after applying to the tooth enamel and only minimally toxic spoke 1 as an adhesive and coating or 15 act on the pulp. In addition, harden, i.e. H. poly- Underfoot in dentistry. merize these connections at a rate generally less than 2 minutes e.g. B. in 10 to 60 seconds at normal body temperature